甘油
催化作用
吸附
插层(化学)
化学
无机化学
化学工程
电催化剂
电化学
密度泛函理论
氧气
法拉第效率
选择性
材料科学
石墨
乙醇酸
傅里叶变换红外光谱
析氧
表面工程
活动中心
红外光谱学
氧化还原
协同催化
作者
Sheng Zhong,Shuang Wei,Bin He,Ruirui Wang,Syed Ali Haider Zaidi,Hasnain Nawaz,Haozhan Chu,Ruixia Liu
出处
期刊:ACS Catalysis
[American Chemical Society]
日期:2025-10-13
卷期号:15 (21): 17738-17750
被引量:5
标识
DOI:10.1021/acscatal.5c05731
摘要
Transforming glycerol into glycolic acid through electrocatalysis offers a strategy for valorizing surplus glycerol and alleviating the energy dilemma. However, it remains challenging to precisely control the oxidation of the hydroxyl functional group and the fracture of the C–C bond. Herein, we develop an interface engineering strategy utilizing potassium graphite intercalation compounds (K-GIC) to modulate Co3O4, achieving significantly enhanced performance in producing glycolate from the electrocatalytic glycerol oxidation reaction (GOR). Specifically, the interfacial charge transfer from electron-rich KCx to Co3O4 increases the electronic density of Co and O atoms. Meanwhile, more oxygen vacancies were generated on Co3O4 due to the electronic effect and lattice distortion. Consequently, the markedly enhanced adsorption capacities and modulated adsorption ratio of glycerol and reactive oxygen species OH– are determined on the catalytic interface. As a result, while the surface catalytic activity is enhanced, the deep oxidation of glycerol and secondary C–C cleavage are weakened, which is beneficial for the generation of glycolate. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations further unlock the decrease in the energy barrier in the pathway toward glycolate. The KCx-Co3O4 exhibits high glycolate selectivity and faradaic efficiency, reaching 44% and 37%, respectively, with a glycerol conversion of 97%. This work provides practical guidance for interface engineering in designing catalysts for value-added glycerol electrooxidation.
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